The dominant nature of Herzberg-Teller terms in the photophysical description of naphthalene compared to anthracene and tetracene

Abstract

The first order and second order corrected photoluminescence quantum yields are computed and compared to experiment for naphthalene in this manuscript discussing negative results. Results for anthracene and tetracene are recalled from previous work (Manian et al. in J Chem Phys 155:054108, 2021), and the results for all three polyacenes are juxtaposed to each other. While at the Franck-Condon point, each of the three noted polyacenes were found to possess a quantum yield near unity. Following the consideration of Herzberg-Teller effects, quantum yields stabilised for anthracene and tetracene to 0.19 and 0.08, respectively. Conversely, the second order corrected quantum yield for naphthalene was found to be 0.91. Analysis of this result showed that while the predicted non-radiative pathways correlate well with what should be expected, the approximation used to calculate second order corrected fluorescence, which yielded very positive results for many other molecular systems, here is unable to account for strong second order contributions, resulting in a grossly overestimated rate of fluorescence. However, substitution of an experimental radiative rate results in a quantum yield of 0.33. This work extols the importance of Herzberg-Teller terms in photophysical descriptions of chromophores, and highlights those cases in which a treatment beyond the above approximation is required.

Figure 1

Schematic representation of (A) naphthalene, (B) anthracene, and (C) tetracene.

Figure 2

Highest occupied (lowest unoccupied) molecular orbitals HOMO (LUMO) for naphthalene, anthracene, and tetracene.

Figure 3

Calculated emission spectra of (A) naphthalene, (B) anthracene, and (C) tetracene. Solvation in cyclohexane was simulated via a PCM at both the Franck–Condon (Red) and Herzberg–Teller (Blue) levels. Spectra are normalised by intensity, and as such are not to scale. (B,C) were taken from Ref. with permissions.

Figure 4

Calculated second-order corrected emission spectra using Orca (red). Reference second-order corrected emission spectra taken from Fig. 3A (blue). Spectra are normalised by intensity, and as such are not to scale.